Construction of Polymer Recycling System Based on Equilibrium Polymerization

基于平衡聚合的聚合物回收系统构建

• 批准号: 10305067
• 负责人: ENDO Takeshi
• 金额: $ 10.18万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10305067/
• 关键词: equilibrium polymerization; polymer recycling; bicyclic monomer; spiro orthoester; bicyclo orthoester; crosslinking; single ring-opening; decrosslinking; 平衡重合

This work dealt with (1) cationic equilibrium polymerization of spiro orthoesters (SOEs) and bicyclo orthoester (BOEs), (2) depolymerization of the obtain polymers, (3) reversible cationic crosslinking and decrosslinking between bifunctional SOEs and BOEs and the network polymers, (4) reversible cationic crosslinking and decrosslinking between SOE and BOE-based linear polymers and network polymers. SOEs gave poly(cyclic orthoester)s by single ring-opening polymerization in the presence of acid catalysts, and this process underwent equilibrium polymerization. We applied the function of equilibrium polymerization to chemical recycling of polymeric materials. Dithiollinked bifunctional spiro orthoester monomers afforded the corresponding crosslinked polymers at 0℃ in the presence of CFィイD23ィエD2COィイD22ィエD2H in bulk, and the resulted crosslinked polymers were efficiently converted into the original bifunctional spiro orthoesters by decrosslinking at room temperature in the presence of CFィイD23ィエD2COィイD22ィエD2H in CHィイD22ィエD2ClィイD22ィエD2. Further, acid-catalyzed reversible crosslinking-decrosslinking of a polymer having a spiro orthoester group in the side chain was carried out. The copolymer obtained by the radical copolymerization of 2-methylene-1,4,6-trioxaspiro[4.6]undecane with acrylonitrile was treated with CFィイD23ィエD2COィイD22ィエD2H at -10℃ in CHィイD22ィエD2ClィイD22ィエD2 to afford the crosslinked polymer quantitatively.The crosslinked polymer was then treated with CFィイD23ィエD2COィイD22ィエD2H at room temperature at a low concentration in CHィイD22ィエD2ClィイD22ィエD2 to recover the original polymer.

本文研究了（1）螺环原酸酯（SOE）和双环原酸酯（BOE）的阳离子平衡聚合，（2）所得聚合物的解聚，（3）双官能度SOE和BOE与网络聚合物的可逆阳离子交联和解交联，（4）SOE和BOE基线性聚合物和网络聚合物的可逆阳离子交联和解交联。在酸性催化剂存在下，SOE通过单开环聚合得到聚环原酸酯，该过程经历平衡聚合。我们将平衡聚合的作用应用于高分子材料的化学回收。二硫醇连接的双官能螺环原酸酯单体在0℃下，在本体存在下，得到相应的交联聚合物，并且所得交联聚合物在室温下，在CH = D22 = CH此外，进行侧链中具有螺环原酸酯基的聚合物的酸催化可逆交联-脱交联。通过2-亚甲基-1，4，在-20 ℃下，用CF 3-D23-D2CO-D22-D2 H处理具有丙烯腈的6-三氧杂螺[4.6]十一烷。将交联聚合物在室温下用低浓度的CF_（23）D_2CO_（22）D_2H处理在CH ↓ [2] D22 ↓ [2] D2Cl ↓ [2] D22 ↓ [2] D2中，以回收原始聚合物。

项目成果

Kiyoko Yoshida, Fumio Sanda, and Takeshi Endo: "Synthesis and Cationic Ring-Opening Polymerization of Mono- and Bifunctional Spiro Orthoesters Containing Ester Groups and Depolymerization of the Obtained Polymers : An Approach to Chemical Recycling for Po

Kiyoko Yoshida、Fumio Sanda 和 Takeshi Endo：“含有酯基的单官能和双官能螺原酸酯的合成和阳离子开环聚合以及所得聚合物的解聚：一种化学回收聚合物的方法

M.Hitomi,F.Sanda,and T.Endo: "First Observation of the Equilibrium Polymerization of a Bicyclo Ortho Ester" J.Polym.Sci.,Part A:Polym.Chem.36. 2823-2825 (1998)

M.Hitomi、F.Sanda 和 T.Endo：“双环原酯平衡聚合的首次观察”J.Polym.Sci.，A 部分：Polym.Chem.36。

遠藤剛、三田文雄: "新しいケミカルリサイクルシステムの構築"ケミカルエンジニアリング. 44. 111-116 (1999)

Tsuyoshi Endo、Fumio Mita：“新型化学品回收系统的构建”《化学工程》44. 111-116 (1999)。

M.Hitomi,F.Sanda and T.Endo: "Reversible Crosslinking-Decrosslinking of Polymers Having Bicyclo Orthester Moieties in the Side Chains"Macromol. Chem. Phys.. 200. 1268-1273 (1999)

M.Hitomi、F.Sanda 和 T.Endo：“侧链中具有双环原酸酯部分的聚合物的可逆交联-解交联”Macromol。

K. Yoshida, F. Sanda, and T. Endo: "Synthesis and Cationic Ring-Opening Polymerization of Mono and Bifunctional Spiro Orthoesters Containing Ester Groups, and Depolymerization of the Obtined Polymers"J. Polym, Sci., Part A : Polym. Chem. 37. 2551-2558 (19

K. Yoshida、F. Sanda 和 T. Endo：“含酯基的单官能和双官能螺原酸酯的合成和阳离子开环聚合，以及所得聚合物的解聚”J。